EP3583091B1 - Composés de dispositifs optiquement actifs - Google Patents

Composés de dispositifs optiquement actifs Download PDF

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EP3583091B1
EP3583091B1 EP18703798.1A EP18703798A EP3583091B1 EP 3583091 B1 EP3583091 B1 EP 3583091B1 EP 18703798 A EP18703798 A EP 18703798A EP 3583091 B1 EP3583091 B1 EP 3583091B1
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atoms
formula
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linear
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EP3583091A1 (fr
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Martin SCHRAUB
Lars Dobelmann-Mara
Stefan RIEDMUELLER
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Merck Patent GmbH
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Merck Patent GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/12—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
    • C07D307/83—Oxygen atoms
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/14—Eye parts, e.g. lenses, corneal implants; Implanting instruments specially adapted therefor; Artificial eyes
    • A61F2/16—Intraocular lenses
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
    • C07D209/32—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C07D307/80—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
    • C07D333/64—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses

Definitions

  • the present invention relates to novel compounds, particularly to compounds comprising a photoactive unit, said novel compounds being particularly suitable for compositions and ophthalmic devices as well as to compositions and ophthalmic devices comprising such compounds.
  • Cataract is a general term for an affection of the eye that leads to a loss of vision and in the extreme to blindness by clouding of the normally clear lens of the eye. It is the major cause of blindness in the world, affecting more than 100 million people. Due to the fact that its major cause is age and the population's average age is increasing, it is expected that the number of cataracts will continue to increase substantially in the future.
  • Intraocular lens Effective treatment of cataract is only possible by surgical intervention, whereby the natural lens of the eye is removed through an incision in the cornea and replaced with an artificial lens, often also referred to as "intraocular lens".
  • intraocular lens an artificial lens
  • current state-of-the-art surgical methods employ eye mapping so as to approximate the refractive power best suited to the respective patient.
  • cataract surgery is one of the most widely used and safest surgical procedures it is not without specific post-surgery problems.
  • the refractive power of the implanted intraocular lens (IOL) is insufficient for restoring good vision.
  • Such problems may, for example, be caused by changes in eye geometry as consequence of the surgery as well as irregular wound healing and positioning errors that result in the artificial lens not having the optimal optical properties.
  • the patient will still require corrective vision aids, e.g. glasses, to be able to see correctly.
  • the resulting refractive power of the implanted artificial lens is so far removed from the required refractive power that further surgery will be required. Particularly for aged persons this is not desirable because the body's capability for healing is reduced with increasing age.
  • there is the risk of attracting endophthalmitis, an inflammation of the eye which can even lead to a complete loss of vision or worse, loss of the eye.
  • WO 2016/200401 A1 describes liquid crystal materials having photoalignment properties.
  • Teflon AF® Poly(methyl methacrylate) intraocular lenses (IOLs) that were coated with Teflon AF®, an amorphous, transparent, and highly hydrophobic fluorocarbon polymer is known from Jean-Marc technikis, J Cataract Refract Surg. 1998, 24, 371-379 .
  • Teflon AF® (Dupont de Nemours) is a poly(tetra-fluoroethylene co-hexafluoro-propyl-2 cyclodethoxydifluoroethylene). Constituted entirely of high-energy bonds, it is stable at temperatures up to 260°C and chemically very resistant. The refractive index is 1.32.
  • PMMA IOL model 808A, Kabi Pharmacia Production B.V.
  • C 8 F 18 fluorocarbon solvent
  • the compounds disclosed therein suffer from being too stiff and too brittle so that they can't be rolled or folded and are thus not fit to be implanted by state of the art cataract surgical methods, particularly by state of the art micro-incision cataract surgical methods.
  • the invention relates to compounds of formula (I) wherein
  • the invention relates further to compositions comprising at least one of said compounds of formula (I) and/or their polymerized forms as well as to articles comprising at least one polymerized compound of formula (I).
  • the invention relates to a process for forming such article, said process comprising the steps of
  • the invention relates to a process for changing the optical properties of an article according to the invention, said process comprising the steps of
  • the compounds of formula (I) and all preferred embodiments of compounds of formula (I) according to the present invention include all stereoisomers or racemic mixtures.
  • compounds according to the invention are more stable toward UV-irradiation due to lower absorption range. Furthermore the chemical and hydrolytical stability is higher and given due to their intrinsic chemical nature e.g. due to lack of positions prone to nucleophilic attacks, like sp 2 centers and the absence of cyclic lactone structure motifs, compared to coumarin-type photoactive chromophores.
  • T g glass transition temperatures
  • Polymers used in intraocular lens manufacturing have preferably relative high refractive indices, which enable the fabrication of thinner intraocular lenses.
  • the polymer used in an intraocular lens will have a refractive index greater than about 1.5 and presently most preferably greater than about 1.55.
  • a linear or branched alkyl group having 1 to 10 C atoms denotes an alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 C atoms, for example methyl, ethyl, iso -propyl, n -propyl, iso -butyl, n -butyl, tert -butyl, n -pentyl, 1-, 2- or 3-methylbutyl, 1,1-, 1,2- or 2,2-dimethylpropyl, 1-ethylpropyl, n -hexyl, n- heptyl, n -octyl, ethylhexyl, n -nonyl or n -decyl.
  • a linear or branched alkyl group having 1 to 20 C atoms include all examples for a linear or branched alkyl group having 1 to 10 C atoms including any alkyl group having 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20 C atoms such as n -undecyl, n -dodecyl, n- tridecyl, n -tetradecyl, n -pentadecyl, n -hexadecyl, n -heptadecyl, n -octadecyl, n -nonadecyl and n -eicosyl.
  • partially halogenated alkyl group denotes that at least one H atom of the alkyl group is replaced by F, Cl, Br or I.
  • the alkyl group is partially fluorinated meaning that at least one H atom of the alkyl group is replaced by F.
  • completely halogenated alkyl group denotes that all H atoms of the alkyl group are replaced by F, Cl, Br and/or I.
  • the alkyl group is completely fluorinated meaning that all H atoms of the alkyl group are replaced by F.
  • a preferred completely fluorinated alkyl group is trifluoromethyl.
  • halogenated or preferably fluorinated corresponds additionally to other groups such as a halogenated cycloalkyl group, a halogenated alkoxy group or a halogenated thioalkyl group.
  • a cycloalkyl group having 3 to 6 C atoms includes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl which may be partially or completely halogenated or fluorinated as explained before.
  • a linear or branched alkoxy group having 1 to 20 C atoms denotes an O-alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 C atoms, for example methoxy, ethoxy, iso -propoxy, n- propoxy, iso -butoxy, n -butoxy, tert-butoxy, n -pentyloxy, 1-, 2- or 3-methylbutyloxy, 1,1-, 1,2- or 2,2-dimethylpropoxy, 1-ethylpropoxy, n- hexyloxy, n -heptyloxy, n -octyloxy, ethylhexyloxy, n -nonyloxy, n -decyloxy, n- undecyloxy, n -dodecyloxy, n -tridecyloxy, n -tetradecyloxy, n -
  • a linear or branched thioalkyl group having 1 to 20 C atoms denotes a S-alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 C atoms, for example thiomethyl, 1-thioethyl, 1-thio- iso -propyl, 1-thio- n -propoyl, 1-thio- iso -butyl, 1-thio- n -butyl, 1-thio- tert -butyl, 1-thio- n- pentyl, 1-thio-1-, -2- or -3-methylbutyl, 1-thio-1,1-, -1,2- or -2,2-dimethylpropyl, 1-thio-1-ethylpropyl, 1-thio- n -hexyl, 1-thio- n -heptyl, 1-thio- n- octyl, 1-thio-ethylhexy
  • Preferred alkyl and alkoxy radicals have 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 C atoms.
  • a polymerizable group is a group which can be subject to or can undergo polymerization thus forming an oligomer or a polymer.
  • Polymerization is the process of taking individual monomers and chaining them together to make longer units. These longer units are called polymers.
  • the compounds of formula (I) as described before and preferably described below are suitable monomers.
  • the polymerizable group R 1 once oligomerized or polymerized thus forms or is part of the backbone of the oligomer or polymer comprising polymerized compounds of formula (I).
  • Suitable polymerizable groups contain at least one double bond or at least one triple bond thus forming polymers where the linking is formed via carbon-carbon bonds.
  • a suitable polymerizable group may contain silicon thus forming polysiloxanes or polysilazanes.
  • the suitable polymerizable groups are selected from the group consisting of an alkenyl group of formula (5), wherein
  • a preferred polymerizable group is selected from the group consisting of trimethoxysilyl, triethoxysilyl, diethoxymethylsilyl and the alkenyl group of formula (5) as described before and preferably described below.
  • Aryl with 6 to 14 C atoms is an aryl group preferably selected from the group consisting of phenyl, naphthyl or anthryl, particularly preferably phenyl.
  • linker -[B]- are therefore selected from the group of formulae (B-1) to (B-34), wherein R' and R 0 have a meaning as described before or preferably described below.
  • the invention therefore relates additionally to compounds of formula (I) as described before wherein -[B]- corresponds to formula (1) and (2) and X 1 , X 2 , X 3 and X 4 have a meaning as described before.
  • linker -[B]- corresponds to formula (1) or (2) and X 1 , X 3 and X 4 are CR' and R' has at each occurrence independently a meaning as described before or preferably described below. Therefore, compounds of formula (I) are particularly preferred where the linker -[B]- corresponds to formulae (B-1), (B-3), (B-8) or (B-9).
  • the invention therefore relates additionally to compounds of formula (I) as described before wherein -[B]- corresponds to formula (1) and (2) and X 1 , X 3 and X 4 are CR' and R' has at each occurrence independently a meaning as described before or preferably described below.
  • the invention therefore relates additionally to compounds of formula (I) as described or preferably described before wherein -[B]- corresponds to formula (1) and (2) and X 2 is CR' and R' has at each occurrence independently a meaning as described before or preferably described below.
  • R' is at each occurrence independently selected from the group consisting of H, F, a linear or branched, non-halogenated, partially or completely halogenated alkyl group having 1 to 20 C atoms, a linear or branched hydroxyalkyl group having 1 to 20 C atoms, a non-halogenated, partially or completely halogenated cycloalkyl group having 3 to 6 C atoms, a linear or branched, non-halogenated, partially or completely halogenated alkoxy group having 1 to 20 C atoms, a linear or branched, non-halogenated, partially or completely halogenated thioalkyl group having 1 to 20 C atoms.
  • At least one R' in -[B]- as described before or preferably described before is different from H and is selected from the group consisting of F, a linear or branched, non-halogenated, partially or completely halogenated alkyl group having 1 to 20 C atoms, a non-halogenated, a linear or branched hydroxyalkyl group having 1 to 20 C atoms, partially or completely halogenated cycloalkyl group having 3 to 6 C atoms, a linear or branched, non-halogenated, partially or completely halogenated alkoxy group having 1 to 20 C atoms, a linear or branched, non-halogenated, partially or completely halogenated thioalkyl group having 1 to 20 C atoms.
  • At least two R' are different from H and are independently selected from the group consisting of F, a linear or branched, non-halogenated, partially or completely halogenated alkyl group having 1 to 20 C atoms, a linear or branched hydroxyalkyl group having 1 to 20 C atoms, a non-halogenated, partially or completely halogenated cycloalkyl group having 3 to 6 C atoms, a linear or branched, non-halogenated, partially or completely halogenated alkoxy group having 1 to 20 C atoms, a linear or branched, non-halogenated, partially or completely halogenated thioalkyl group having 1 to 20 C atoms.
  • R' is at each occurrence independently preferably selected from the group consisting of H, F, a linear or branched, non-halogenated, partially or completely halogenated alkyl group having 1 to 10 C atoms, a linear or branched, non-halogenated and a partially or completely halogenated alkoxy group having 1 to 10 C atoms.
  • At least one R' in -[B]- as described before or preferably described before is different from H and is selected from the group consisting of F, a linear or branched, non-halogenated, partially or completely halogenated alkyl group having 1 to 10 C atoms, a linear or branched, non-halogenated and a partially or completely halogenated alkoxy group having 1 to 10 C atoms.
  • At least two R' are different from H and are independently selected from the group consisting of F, a linear or branched, non-halogenated, partially or completely halogenated alkyl group having 1 to 10 C atoms, a linear or branched, non-halogenated and a partially or completely halogenated alkoxy group having 1 to 10 C atoms.
  • R' is at each occurrence independently particularly preferably selected from the group consisting of H, F, methyl, ethyl, n -propyl, n -butyl, n -pentyl, n- hexyl, n -heptyl, n -octyl, trifluoromethyl, pentafluoroethyl, heptafluoropropyl, methoxy, ethoxy, propoxy, trifluoromethoxy and pentafluoroethoxy.
  • R' is at each occurrence independently very particularly preferably selected from the group consisting of H, F, ethyl, n -pentyl, trifluoromethyl, methoxy, and trifluoromethoxy.
  • the invention is further directed to compounds of formula (I) as described before where -[B]- corresponds to formulae (1) to (4) and wherein at least one R' within X 1 , X 2 , X 3 . X 4 , X 6 or X 7 is not H.
  • the invention is further directed to compounds of formula (I) as described before where -[B]- corresponds to formulae (B-1) to (B-29) or (B-31) to (B-34) or to preferred linkers as described before, wherein at least one R' is not H and R 0 has a meaning as described before or preferably described below.
  • the substituent R' within X 1 or X 3 in formula (1) is particularly preferred not H.
  • the substituent R' within X 7 in formula (3) is particularly preferred not H.
  • R 3 , R 4 , R 5 and R 6 are at each occurrence independently R' where R' has a meaning or a preferred or particularly preferred meaning as described before.
  • R 5 is preferably H or F.
  • R 5 is particularly preferably H.
  • R 7 corresponds to R' in case m is 0 wherein R' has a meaning or a preferred or particularly preferred meaning as described before.
  • R 7 corresponds to R' which is not H in case m is 0.
  • R' is preferably not H, it is selected from the preferred group consisting of F, methyl, ethyl, n -propyl, n -butyl, n -pentyl, n -hexyl, n- heptyl, n -octyl, trifluoromethyl, pentafluoroethyl, heptafluoropropyl, methoxy, ethoxy, propoxy, trifluoromethoxy and pentafluoroethoxy or from the particular preferred group consisting of F, ethyl, n -pentyl, trifluoromethyl, methoxy and trifluoromethoxy.
  • the invention is further directed to compounds of formula (I) as described before where -[B]- corresponds to formulae (1) to (4) and wherein at least one R' within X 1 , X 2 , X 3 . X 4 , X 6 or X 7 is not H and R 7 is not H in case m is 0.
  • the invention is further directed to compounds of formula (I) as described before where -[B]- corresponds to formulae (B-1) to (B-29) or (B-31) to (B-34) or to preferred linkers as described before, wherein at least one R' is not H and R 7 is not H in case m is 0 and R 0 has a meaning as described before or as preferably described below.
  • the substituent R 7 corresponds to R 1 in case m is 1 wherein R 1 has a meaning or a preferred meaning as described before or further below.
  • Compounds of formula (I) in which m is 1 are preferred having a linker -[B]- selected from the group consisting of formula (1) to (4) wherein at least one substituent R' within X 1 , X 2 , X 3 , X 4 , X 6 or X 7 is not H and in which at least one substituent R 3 , R 4 or R 6 is not H.
  • the invention is further directed to compounds of formula (I) as described before where -[B]- corresponds to formulae (1) to (4) and wherein at least one R' within X 1 , X 2 , X 3 . X 4 , X 6 or X 7 is not H, in which at least one substituent R 3 , R 4 or R 6 is not H and R 7 corresponds to R 1 in case m is 1.
  • the invention is further directed to compounds of formula (I) as described before where -[B]- corresponds to formulae (B-1) to (B-29) or (B-31) to (B-34) or to preferred linkers as described before, wherein at least one R' is not H, in which at least one substituent R 3 , R 4 or R 6 is not H and R 7 corresponds to R 1 in case m is 1 wherein R 0 and R 1 has a meaning as described before or further below.
  • R 0 is at each occurrence independently preferably methyl, ethyl, iso -propyl, 2-methyl-propyl, n -butyl, n -pentyl, 4-methyl-pentyl or cyclopropyl.
  • R 0 is particularly preferably ethyl, iso -propyl, 2-methyl-propyl, n -pentyl or 4-methyl-pentyl.
  • R 0 is particularly preferably methyl or n -butyl.
  • R 0 is particularly preferably methyl.
  • the compounds of formula (I) as described before or preferably described before contain one polymerizable group R 1 .
  • R 1 polymerizable group
  • Such compounds can be preferably used as monomers for the preparation of a blank which may be transformed to an ophthalmic device such as an eye-implant or specifically an intraocular lens or to the ophthalmic device as such as described before.
  • the invention is therefore additionally directed to compounds of formula (I) wherein n is 1 and m is 0 which can preferably be described according to formula (I') wherein R 1 , -R 2 -, Y, R 3 , R 4 , R 5 , R 6 , X, -[B]- and R 7 have a meaning as described before or preferably described before or below.
  • the invention is therefore additionally directed to compounds of formula (I) wherein n is 0 and m is 1 which can preferably be described according to formula (I") wherein R 1 , -R 2 -, Y, R 3 , R 4 , R 5 , R 6 , X, -[B]- and R 7 have a meaning as described before or preferably described before or below.
  • the compounds of formula (I) as described before or preferably described before contain two polymerizable groups R 1 .
  • R 1 polymerizable groups
  • Such compounds can be preferably used as cross-linking agent for the preparation of a blank which may be transformed to an ophthalmic device such as an eye-implant or specifically an intraocular lens or to the ophthalmic device as such as described before.
  • the invention is therefore additionally directed to compounds of formula (I) wherein n is 1 and m is 1 which can preferably be described according to formula (I'") wherein R 1 , -R 2 -, Y, R 3 , R 4 , R 5 , R 6 , X, -[B]- and R 7 have a meaning as described before or preferably described before or below.
  • Y is at each occurrence independently O, S or a bond.
  • the linking element -R 2 - is selected from the group consisting of -(C(R) 2 ) o -wherein at least one R is F or a linear or branched partially or fully fluorinated alkyl group having 1 to 4 C atoms, -(C(R) 2 ) p -X 8 -(C(R) 2 ) q -(X 9 ) s -(C(R) 2 ) r -(X 10 ) t -(C(R) 2 ) u -, wherein at least one R is F or a linear or branched partially or fully fluorinated alkyl group having 1 to 4 C atoms and a cycloalkylene group having 5 or 6 C atoms which is substituted with at least one R which is F or a linear or branched partially or fully fluorinated alkyl group having 1 to 4 C atoms and o is
  • the linking element -R 2 - is selected from the group consisting of -(C(R) 2 ) o - wherein at least two R are F, -(C(R) 2 ) p -X 8 -(C(R) 2 ) q -(X 9 ) s -(C(R) 2 ) r -(X 10 ) t -(C(R) 2 ) u -, wherein at least two R are F and a cycloalkylene group having 5 or 6 C atoms which is substituted with at least one R which is F or a linear or branched partially or fully fluorinated alkyl group having 1 to 4 C atoms and o, X 8 , X 9 , X 10 , s, t, p, q, r and u have a meaning as described or preferably described before or below.
  • R is at each occurrence independently selected from the group consisting of H, F, a linear or branched alkyl group having 1 to 8 C atoms or a linear or branched partially or fully fluorinated alkyl group having 1 to 4 C atoms.
  • R is preferably at each occurrence independently selected from the group consisting of H, F, methyl, ethyl, n -propyl, isopropyl, n -butyl, n -pentyl, isobutyl, ethylhexyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, trifluoromethyl, pentafluoroethyl, heptafluoropropyl and nonafluorobutyl.
  • R is particularly preferably at each occurrence independently H, F, methyl, 2,2,2-trifluoroethyl or trifluoromethyl.
  • o is selected from the group consisting of 3 to 12, particularly preferably 8 to 12.
  • s is 1.
  • t is 0 or 1.
  • X 8 , X 9 and X 10 are O.
  • p and u are each independently 1, 3, 3, 4, 5 or 6, particularly preferably 1 or 2.
  • q and r are each independently 1, 2 or 3, particularly preferably 1.
  • Suitable examples for -R 2 - are -(CF 2 )-(CH 2 )-, -(CH 2 )-(CF 2 )-, -(CH 2 )-(CF 2 )-(CH 2 )-, -(CH 2 )-(CF 2 )-(CH 2 ) 2 -, - (CH 2 )-(CF 2 )-(CH 2 ) 3 -, -(CH 2 )-(CF 2 )-(CH 2 ) 4 -, -(CH 2 )-(CF 2 )-(CH 2 ) 5 -, -(CH 2 )-(CF 2 )-(CH 2 ) 6 -, -(CH 2 )-(CF 2 )-(CH 2 ) 7 -, -(CH 2 )-(CF 2 )-(CH 2 ) 8 -, -(CH 2 )-(CF 2 )-(CH 2 ) 9 -, -(CH 2 )-
  • Preferred examples for -R 2 - are -(CH 2 ) 3 -(CF 2 )-(CH 2 ) 3 -, -(CH 2 )-(CF 2 ) 3 -(CH 2 )-, -(CH 2 ) 2 -(CF 2 ) 4 -(CH 2 ) 2 -, -(CH 2 )-[CH(CF 3 )]-(CH 2 )-, -(CH 2 )-[C(CH 3 )CF 3 ]-(CH 2 )-, -(CH 2 )-[CH(CH 2 CF 3 )]-(CH 2 )-, -(CH 2 )-[C(CH 3 )(CH 2 CF 3 )]-(CH 2 )-, -(CH 2 ) 2 -(CF 2 )-O-(CF 2 )-O-(CF 2 )-(CH 2 ) 2 -, -(CH 2 )-(CF 2 )-O-(
  • the invention therefore relates to compounds of formula (I), (I'), (I") and (I''') as described before or preferably described before wherein -R 2 - is at each occurrence independently -(C(R) 2 ) o -, wherein at least one R is F or a linear or branched partially or fully fluorinated alkyl group having 1 to 4 C atoms or -(C(R) 2 ) p -X 8 -(C(R) 2 ) q -(X 9 ) s -(C(R) 2 ) r -(X io ) t -(C(R) 2 ) u -, wherein at least one R is F or a linear or branched partially or fully fluorinated alkyl group having 1 to 4 C atoms and all other R, o, X 8 , X 9 , X 10 , s, t, p, q, r and u have a meaning as
  • the linking element -(C(R) 2 ) o - or -(C(R) 2 ) p -X 8 -(C(R) 2 ) q -(X 9 ) s -(C(R) 2 ) r -(X 10 )t-(C(R) 2 ) u - as -R 2 - is particularly preferably selected from the group consisting of -(CH 2 ) 3 -(CF 2 )-(CH 2 ) 3 -, -(CH 2 )-(CF 2 ) 3 -(CH 2 )-, -(CH2)2-(CF2)4-(CH 2 ) 2 -, -(CH 2 )-[CH(CF 3 )]-(CH 2 )-, -(CH 2 )-[C(CH 3 )CF 3 ]-(CH 2 )-, -(CH 2 )-[CH(CH 2 CF 3 )]-(CH 2 )-, -
  • the substituent Y-R 2 -R 1 is particularly preferably selected from the group consisting of O-R 2 -R 1 , -R 2 -R 1 , and S-R 2 -R 1 wherein -R 2 - has a meaning as described before or preferably or particularly preferably described before and wherein R 1 is a polymerizable group selected from the group consisting of a trialkoxysilyl group, a dialkoxyalkylsilyl group, a silyl group of formula (6), (7) or (8) as described before where the alkyl and/or alkoxy groups are each independently linear or branched having 1 to 6 C atoms, or an alkenyl group of formula (5), wherein
  • the substituent Y-R 2 -R 1 is preferably selected from the group consisting of O-R 2 -R 1 , -R 2 -R 1 and S-R 2 -R 1 , wherein -R 2 - is selected from the group consisting of -(CH 2 ) 3 -(CF 2 )-(CH 2 ) 3 -, -(CH 2 )-(CF 2 ) 3 -(CH 2 )-, -(CH 2 ) 2 -(CF 2 ) 4 -(CH 2 ) 2 -, -(CH 2 )-[CH(CF 3 )]-(CH 2 )-, -(CH 2 )-[C(CH 3 )CF 3 ]-(CH 2 )-, -(CH 2 )-[CH(CH 2 CF 3 )]-(CH 2 )-, -(CH 2 )-[C(CH 3 )(CH 2 )-, -(CH 2 )-[CH(CH
  • R 9 and R 10 are H.
  • R 8 is H, methyl, ethyl or phenyl.
  • Preferred alkenyl groups of formula (5) are therefore represented by any one selected from the group consisting of formulae (5-1), (5-2), (5-3), (5-4), (5-5), (5-6), (5-7), (5-8), and (5-9):
  • the alkenyl group represented by formula (5-1) is called methacrylate.
  • the alkenyl group represented by formula (5-2) is called acrylate.
  • the preferred groups R 1 are preferably combined with preferred groups of the linking element -R 2 - and/or the linking element Y-R 2 -. Combinations are excluded where two O atoms or one O atom and one S atom are directly bonded to each other as known for a skilled artisan in the field of organic chemistry.
  • the substituent Y-R 2 -R 1 is therefore particularly preferably selected from the group consisting of O-(CH 2 ) 3 -(CF 2 )-(CH 2 ) 3 -R 1 , O-(CH 2 )-(CF 2 ) 3 -(CH 2 )-R 1 , O-(CH 2 ) 2 -(CF 2 ) 4 -(CH 2 ) 2 -R 1 , O-(CH 2 )-[CH(CF 3 )]-(CH 2 )-R 1 , O-(CH 2 )-[C(CH 3 )CF 3 ]-(CH 2 )-R 1 , O-(CH 2 )-[CH(CH 2 CF 3 )]-(CH 2 )-R 1 , O-(CH 2 )-[C(CH 3 )(CH 2 CF 3 )]-(CH 2 )-R 1 , O-(CH 2 )-[C(CH 3 )(CH 2 CF 3 )]
  • the compounds of formula (I), (I'), (I") and (I''') comprise a polymerizable group R 1 which is a methacryl or an acryl group represented by formula (5-1) and (5-2).
  • the invention therefore relates further to compounds of formula (I), (I'), (I") and/or (I''') as described before or preferably described before wherein R 1 is at each occurrence independently an acryl or methacryl group.
  • Examples for compounds of formula (I), (I'), (I") and/or (I''') are the following compounds O-001 to 0-289, S-001 to S-169 and N-001 to N-172:
  • the compounds of the present application may be synthesized by methods well known to the skilled person. Preferably, all syntheses are carried out under an inert atmosphere using dried solvents.
  • the first type of reaction is a classic aldol-addition with subsequent decarboxylation.
  • the second type of reaction is a Palladium catalyzed Suzuki reaction.
  • the third type of reaction is an ether cleavage in the presence of borontribromide.
  • the fourth type of reaction is a Williamson ether synthesis.
  • the fifth type of reaction is an esterification reaction.
  • the first type of reaction is a classical ring closure via nucleophilic substitution, aldol-addition followed by decarboxylation.
  • a pentyl substituent is introduced via palladium-catalyzed Suzuki reaction.
  • the third type of reaction is an ether cleavage in the presence of borontribromide.
  • the fourth type of reaction is a Williamson ether synthesis followed by an esterification reaction.
  • the first type of reaction is a Sonogashira reaction followed by a ring closure in the presence of Zinc bromide.
  • an alkyl group on the N atom is introduced via alkyl iodide.
  • the third type of reaction is an ether cleavage in the presence of borontribromide.
  • the fourth type of reaction is a Williamson ether synthesis followed by an esterification reaction.
  • the compounds of formula (I), (I'), (I") and/or (I''') as described before or preferably described before contain a polymerizable group and are predestinated as monomers for an oligomerization or a polymerization.
  • the invention is therefore further directed to an oligomer or polymer comprising polymerized compounds of formula (I), (I'), (I") and/or (I''') as described before or preferably described before.
  • polymer generally means a molecule of high relative molecular mass, the structure of which essentially comprises the multiple repetition of units derived, actually or conceptually, from molecules of low relative molecular mass ( PAC, 1996, 68, 2291 ).
  • polymer includes homopolymers and co-polymers.
  • oligomer generally means a molecule of intermediate relative molecular mass, the structure of which essentially comprises a small plurality of units derived, actually or conceptually, from molecules of lower relative molecular mass ( PAC, 1996, 68, 2291 ). In a preferred sense a polymer means a compound having ⁇ 30 repeating units, and an oligomer means a compound with > 1 and ⁇ 30 repeating units.
  • an asterisk denotes a linkage to the adjacent repeating unit in the polymer chain or oligomer chain or to a terminal end group.
  • Suitable terminal end groups are known to the skilled artisan and depend on the polymerization method used.
  • repeating unit and “monomeric unit” mean the constitutional repeating unit (CRU), which is the smallest constitutional unit the repetition of which constitutes a regular macromolecule, a regular oligomer molecule, a regular block or a regular chain ( PAC, 1996, 68, 2291 ).
  • CRU constitutional repeating unit
  • the molecular weight is given as the number average molecular weight M n or weight average molecular weight Mw, which is determined by gel permeation chromatography (GPC) against polystyrene standards in eluent solvents such as tetrahydrofuran, trichloromethane (TCM, chloroform), chlorobenzene or 1,2,4-trichlorobenzene. Unless stated otherwise, tetrahydrofuran is used as solvent.
  • the total number of repeating units n is seen preferably ⁇ 30, very preferably ⁇ 100, most preferably ⁇ 200, and preferably up to 5000, very preferably up to 3000, most preferably up to 2000, including any combination of the aforementioned lower and upper limits of n.
  • the polymers of the present invention include homopolymers, statistical co-polymers, random co-polymers, alternating co-polymers and block co-polymers, and combinations of the aforementioned.
  • the polymerizable group R 1 forms the regioregular, alternated, regiorandom, statistical, block or random homopolymer or co-polymer backbone or is part of the polymer backbone where R 1 has a meaning as described or preferably described before.
  • such oligomer or polymer comprises a constitutional unit M 0 of formulae (5-p-1), (5-p-2), (5-p-3) wherein -R 2 -, Y, R 3 , R 4 , R 5 , R 6 , X, -[B]-, R 7 , X 11 , R 8 , R 9 , R 10 and c have a meaning or a preferred meaning as described or preferably described before.
  • Combinations are excluded where two O atoms or an O atom and a S atom are directly linked to each other as known for a skilled artisan in the field of organic chemistry.
  • the co-polymer may be an oligomer or polymer comprising one or more polymerized compounds of formula (I), (I'), (I") or (I''') or a constitutional unit M 0 of formulae (5-p-1), (5-p-2), (5-p-3), which may be the same or different from one another, and one or more constitutional units M 2 , which may be the same or different from one another. Said one or more constitutional units M 2 are chemically different from the units M 0 .
  • said one or more constitutional units M 2 are derived by polymerization of one or more monomers selected from the group consisting of styrene, ethoxyethyl methacrylate (EOEMA), methyl methacrylate (MMA), n-alkyl methacrylates (the n-alkyl groups comprising 2-20 C-atoms), n-alkyl methacrylates (the n-alkyl groups comprising 2-20 C-atoms), ethoxyethoxy ethylacrylate (EEEA), 2-hydroxyethyl methacrylate (HEMA), tetrahydrofuryl methacrylate (THFMA), glycidylmethacrylate (GMA), 16-hydroxyhexadecyl acrylate, 16-hydroxyhexadecyl methacrylate, 18-hydroxyoctadecyl acrylate, 18-hydroxyoctadecyl methacrylate, 2-phenoxyethyl acrylate (
  • said one or more constitutional units M 2 are derived by polymerization of one or more monomers selected from the group consisting of styrene, ethoxyethyl methacrylate (EOEMA), methyl methacrylate (MMA), n-alkyl methacrylates (the n-alkyl groups comprising 2-20 C-atoms), ethoxyethyl methacrylate (EOEMA), methyl methacrylate (MMA), ethoxyethoxy ethylacrylate (EEEA), 2-hydroxyethyl methacrylate (HEMA), tetrahydrofuryl methacrylate (THFMA), glycidylmethacrylate (GMA), 16-hydroxyhexadecyl acrylate, 16-hydroxyhexadecyl methacrylate, 18-hydroxyoctadecyl acrylate, 18
  • said one or more constitutional units M 2 are derived by polymerization of one or more monomers selected from the group consisting of trialkoxyalkenylsilane, dialkoxyalkylalkenylsilane or a silane of formula (9) and (10), where the alkyl and/or alkoxy groups are at each occurrence independently of each other linear or branched having 1 to 6 C atoms and where the alkenyl group is at each occurrence independently linear having 2 to 4 C atoms in combination with inventive monomers containing a polymerizable group containing at least one Si atom.
  • the oligomer or polymer according to the invention is a homopolymer, i.e. an oligomer or polymer comprising one or more constitutional unit M 0 of formulae (5-p-1), (5-p-2), (5-p-3), wherein all constitutional units M 0 are the same.
  • Exemplary polymeric compounds may be selected from the following formulae (P-001) to (P-628):
  • n gives the degree of polymerization as explained before.
  • a co-polymer according to the invention as described before or preferably described before comprises the one or more constitutional units M 0 in a molar ratio m1 and the one or more constitutional units M 2 in a molar ratio m2, wherein the ratio m1 : m2 is at least 0.01 and at most 100.
  • oligomers or polymers according to the invention as described before or preferably described may be cross-linked.
  • the oligomers and polymers of the present invention may be made by any suitable method. It is, however, preferred that the present oligomers and polymers are made by radical polymerization, wherein the polymerization reaction is started by means of a suitable radical polymerization initiator.
  • a suitable radical polymerization initiator is not particularly limited and may be any suitable radical generating compound. Such compounds are well known to the skilled person.
  • Suitable polymerization initiators comprising one or more peroxide groups may, for example, be selected from the groups consisting of t-butyl(peroxy-2-ethyl-hexanoate), di-(tert-butylcyclohexyl)peroxydicarbonate and benzoyl peroxide.
  • Suitable polymerization initiators comprising one or more azo groups may, for example, be selected from the group consisting of 1,1'-azobis(cyclohexancarbonitrile) and 2,2'azobis(cyclohexanecarbonitrile) (AIBN).
  • a suitable example of a photoinitiator is dimethylaminobenzoate /camphorquinone.
  • the wavelength required to decompose said photoinitiator is different from the wavelength needed to irradiate the compound of the present application so as to change its optical properties.
  • the radical initiators are used in an amount of at least 0.0001 eq and of at most 0.1 eq of the main monomer.
  • Such radical initiators could be thermal initiators, e.g. azobisisobutyronitrile (AIBN) or photochemical initiators like dimethylaminobenzoate/camphorquinone.
  • the present invention is also directed to a composition
  • a composition comprising at least one compound of formula (I), (I'), (I") or (I''') as described or preferably described before and/or an oligomer or polymer as described before or preferably described before.
  • a composition comprising at least one compound of formula (I), (I'), (I") or (I''') as described or preferably described before and an oligomer or polymer as described before is primarily used for the synthesis of block co-polymers with the condition that the oligomer or polymer has at least one reactive group left which may react with the monomers.
  • composition may comprise further different components.
  • further components may, for example, be selected from the group consisting of UV absorbers, antioxidants and cross-linkers.
  • compositions may include or comprise, essentially consist of or consist of the said requisite or optional constituents. All compounds or components which can be used in the compositions are either known and commercially available or can by synthesized by known processes.
  • UV absorber that may be used in the present composition is not particularly limited and can easily be selected from those generally known to the skilled person.
  • suitable UV absorbers are characterized by being unsaturated compounds, preferably compounds comprising one or more selected from group consisting of olefinic groups, aryl groups and heteroaryl groups; these groups may be present in any combination.
  • Suitable UV-absorbers for use in the present composition may, for example, be selected from those comprising a group selected from benzotriazole, benzophenone and triazine.
  • Suitable UV-absorbers are, for example, disclosed in U.S. Pat. Nos. 5,290,892 ; 5,331,073 and 5,693,095 .
  • Suitable cross-linkers may be used to impart elastomeric properties to the present composition and the articles produced therewith.
  • any suitable di- or tri-functional monomer may be used as crosslinker.
  • Such monomers are generally well known to the skilled person including at least one compound of formula (I''') as described before or preferably described before.
  • Preferred cross-linker may be selected from the following group of compounds Ethylene glycol dimethacrylate (EGDMA) is particularly preferred.
  • EGDMA Ethylene glycol dimethacrylate
  • Suitable antioxidants are phenyl acrylate derivatives bearing a hindered phenol moiety.
  • a preferred antioxidant is
  • the compounds of formula (I) according to the invention and their oligomers or polymers as described before or preferably described before are particularly well suited for use in optically active devices.
  • the present invention is also directed to articles e.g. blanks which may be transformed into optically active devices comprising at least one compound of formula (I) as described before or preferably described before or at least one oligomer or polymer as described before or preferably described before.
  • Preferred articles are blanks which may be transformed into optically active devices or the optically active devices as such.
  • Preferred optically active devices are ophthalmic devices. Examples of such ophthalmic devices include lenses, keratoprostheses, and cornea inlays or rings. More preferably, said article is a blank which may be transformed into an eye-implant or the eye-implant as such. More preferably, said eye-implant is a lens. Most preferably, such article is a blank which may be transformed into an intraocular lens or the intraocular lens as such, which may, for example, be a posterior chamber intraocular lens or an anterior chamber intraocular lens.
  • a blank of this invention may be produced as a step in the manufacturing process used to create an intraocular lens.
  • a manufacturing process may include the steps of polymer synthesis, polymer sheet casting, blank cutting, optic lathe cutting, optic milling, haptic milling or attachment, polishing, solvent extraction, sterilization and packaging.
  • present articles according to the invention as described before or preferably described before may be formed by a process comprising the steps of
  • Intraocular lenses in accordance with the present invention are believed to show particularly advantageous properties in that they are flexible enough so as to be rolled or folded and consequently requiring a much smaller incision for them to be inserted into the eye. It is believed that this will allow for improved healing of the eye, particularly in respect to the time for the eye to heal.
  • the type of intraocular lens is not limited in any way. It may, for example, comprise one or more optic and one or more haptic components, wherein the one or more optic components serve as lens and the one or more haptic components are attached to the one or more optic components and hold the one or more optic components in place in the eye.
  • the present intraocular lens may be of a one-piece design or of multi-piece design, depending on whether the one or more optic components and the one or more haptic components are formed from a single piece of material (one-piece design) or are made separately and then combined (multi-piece design).
  • the present intraocular lens is also designed in such a way that it allows to be, for example, rolled up or folded small enough so that it fits through an incision in the eye, said incision being as small as possible, for example, at most 3 mm in length.
  • intraocular lenses in accordance with the present invention allow for the non-invasive adjustment of the optical properties, particularly the refractive power, after implantation of the lens into the eye, thus reducing the need for post-surgery vision aids or reducing or totally avoiding follow-up surgery.
  • the present invention is also directed to a process of changing the optical properties of an article as defined or preferably defined herein, said process comprising the steps of
  • said irradiation has a wavelength of at least 250 nm or 300 nm, more preferably of at least 350 nm, even more preferably of at least 400 nm, still even more preferably of at least 450 nm, and most preferably of at least 500 nm.
  • said irradiation has a wavelength of at most 1400 nm or 1300 nm or 1200 nm or 1100 nm or 1000 nm, more preferably of at most 950 nm or 900 nm, even more preferably of at most 850 nm, still even more preferably of at most 800 nm and most preferably of at most 750 nm.
  • DCM is used to denote dichloromethane.
  • DMF is used to denote dimethylformamide.
  • EE is used to denote ethyl acetate.
  • THF is used to denote tetrahydrofuran.
  • Co-polymer-properties can be investigated on blanks, prepared by bulk polymerization of the monomers. Co-monomers, cross-linkers and initiators therefore can be purchased from commercial sources. All chemicals are of highest purity available and can be used as received.
  • GSP 1 General remarks & general synthetic procedures (GSP 1) for the reduction of aliphatic diesters or diketones to the corresponding diols:
  • Solid, fine powdered lithiumaluminium hydride (2.0 - 5.0 equiv.) is suspended in dry THF at room temperature.
  • the corresponding diacid- or diester derivative is dissolved in dry THF and the solution is slowly added dropwise to the lithiumaluminium slurry while cooling with an ice bath.
  • the reaction solution is warmed to room temperature and the consumption of the starting material is checked by TLC.
  • the suspension is carefully quenched with 2M H 2 SO 4 , additional water is added. For a better workup, the suspension should have a pH of ⁇ 7.
  • the phases are separated and extracted with Et 2 O.
  • the organic phase is washed with H 2 O, dried over MgSO 4 and evaporated under reduced pressure.
  • GSP 4 General remarks & general synthetic procedures (GSP 4) for the synthesis of 2-phenyl-benzofurans from hydroxy-benzaldehyde derivatives or dimethyl-thiocarbamic acid 4-formyl-3-hydroxy-phenyl ester derivatives with methyl 2-bromo-2-(4-bromophenyl)acetate:
  • R1 means reactant 1
  • R2 means reactant 2
  • [P] means product No. Yield [%] 4a R1 R2 [P] 39
  • 4d R1 R2 [P] 69
  • 4e R1 R2 [P] 62
  • 4g R1 R2 [P] 57 4h R1 R2 [P] 49 4i R1 R2 [P] 44 4j R1 R2 [P] 52 4k R1 R2 [P] 32
  • the cooled reaction mixture is diluted with ethyl acetate and HCI solution (2 M). The solution is transferred to a separatory funnel. The organic phase is extracted with HCI solution (2 M) and water and brine. The organic phase is dried over MgSO 4 , filtered and concentrated under reduced pressure. The residue is purified by silica gel column chromatography (heptane/ethyl acetate [5/1]) to yield 6-Methoxy-2-(4-pentyl-phenyl)-benzofuran (350 mg, 1.2 mmol, 66% of theory).
  • R1 means reactant 1
  • R2 means reactant 2
  • [P] means product No. Yield [%] 5a R1 R2 [P] 75 5b R1 R2 [P] 80 5c R1 R2 [P] 72 5d R1 R2 [P] 73 5e R1 R2 [P] 92 5f R1 R2 [P] 60
  • the obtained light brown oil is purified using silica gel chromatography (chloroform/methanol; 30/1) to afford 2-(2-ethyl-4-pentylphenyl)benzofuran-6-thiol (400.00 mg, 1.1 mmol, 53 % of theory).
  • R1 means reactant 1
  • R2 means reactant 2
  • [P] means product No. 7a
  • R1 R2 [P] 7g R1 R2 [P] 7h
  • the bromo-functionalized derivatives of the corresponding diols are prepared in advance through reaction of the corresponding diol with HBr in refluxing toluene.
  • 3,3,4,4,5,5,6,6-octafluoro-8-((2-(4-pentyl-2-(trifluoromethoxy)phenyl)benzofuran-6-yl)thio)octan-1-ol can be isolated in 76% yield (of theory) as a pale beige solid.
  • the corresponding aliphatic alcohol is dissolved in dry THF and the solution is cooled with an ice-bath. Triethylamine (4.00 equivs.) is added and the solution is stirred for a few minutes. Then acryloyl chloride or methacryloyl chloride (1.05 - 2.00 equivs.) is added at ice-bath temperature, while precipitating a colourless solid. The solution is stirred for several hours and is monitored via TLC. Upon completion of the reaction, the suspension is filtrated and washed with THF. The filtrate is evaporated under reduced pressure and purified via column chromatography using cyclohexane / ethyl acetate.
  • the corresponding monomer is dissolved in dry N,N-dimethylformamide in a Schlenck-tube with a stirring bar.
  • the solution is degassed performing three times freeze-evacuate-thaw cycles.
  • azoisobutyronitrile AIBN, 0.05 equiv.
  • AIBN azoisobutyronitrile
  • the solution is cooled to room temperature and is then poured dropwise into cold methanol (100 ml methanol / 100 mg monomer) while stirring.
  • the precipitated polymer is collected on a frit or the solution is centrifuged several times to obtain the final polymer material.
  • the cooled reaction mixture is diluted with ethyl acetate and HCI solution (2 M). The solution is transferred to a separatory funnel. The organic phase is extracted with HCI solution (2 M) and water and brine. The organic phase is dried over MgSO 4 , filtered and concentrated under reduced pressure. The residue is purified by silica gel column chromatography (heptane/ethyl acetate [5/1]) to yield 6-methoxy-2-(4-pentylphenyl)benzo[b]thiophene (390 mg, 1.26 mmol, 84 % of theory).
  • 6-Methoxy-2-phenyl-benzo[b]thiophene (780.00 mg, 3.25 mmol) is dissolved in Dichloromethane (anhydrous) (20.73 ml, 324.57 mmol) and cooled to 5 °C.
  • Boron tribromide (369.60 ⁇ l, 3.89 mmol) is added dropwise to this solution over the course of 10 min, and stirring is continued for 2 h.
  • the reaction mixture is subsequently slowly poured into water, and the organic phase is diluted with ethyl acetate, washed three times with water, dried over MgSO 4 , evaporated in a rotary evaporator.
  • R means reactant
  • [P] means product No. Yield [%] 13a
  • R1 means reactant 1
  • R2 means reactant 2
  • [P] means product No. 14a R1 R2 [P] 14b R1 R2 [P] 14c R1 R2 [P] 14d R1 R2 [P] 14e R1 R2 [P] 14f R1 R2 [P] 14g R1 R2 [P] 14h R1 R2 [P]
  • the corresponding aliphatic alcohol is dissolved in dry THF and the solution is cooled with an ice-bath. Triethylamine (4.00 equivs.) is added and the solution is stirred for a few minutes. Then acryloyl chloride or methacryloyl chloride (1.05 - 2.00 equivs.) is added at ice-bath temperature, while precipitating a colourless solid. The solution is stirred for several hours and is monitored via TLC. Upon completion of the reaction, the suspension is filtrated and washed with THF. The filtrate is evaporated under reduced pressure and purified via column chromatography using cyclohexane / ethyl acetate.
  • R means reactant
  • [P] means product No. 15a
  • 15f R [P] 15g
  • the corresponding monomer is dissolved in dry N,N-dimethylformamide in a Schlenck-tube with a stirring bar.
  • the solution is degassed performing three times freeze-evacuate-thaw cycles.
  • azoisobutyronitrile AIBN, 0.05 equiv.
  • AIBN azoisobutyronitrile
  • the solution is cooled to room temperature and is then poured dropwise into cold methanol (100 ml methanol / 100 mg monomer) while stirring.
  • the precipitated polymer is collected on a frit or the solution is centrifuged several times to obtain the final polymer material.
  • R1 means reactant 1
  • R2 means reactant 2
  • [P] means product No. Yield [%] 19a
  • 19b means reactant 2
  • [P] means product No. Yield [%] 19a
  • 19b means reactant 2
  • [P] means product No. Yield [%] 19a
  • 19b 19b
  • 19c means R1 R2 [P] 74
  • R1 R2 [P] 85 19e
  • 6-Methoxy-1-methyl-2-phenylindole (184 mg, 775 ⁇ mol) is dissolved in dichloromethane (10 ml) and cooled to 5 °C. Boron tribromide (96.6 ⁇ l, 1.0 mmol) are added dropwise to this solution, and stirring is continued overnight. Water is subsequently slowly added to the mixture, and the organic phase is diluted with ethyl acetate, washed three times with water, dried over MgSO 4 , evaporated under reduced pressure and filtered through a pad of silica gel with dichloromethane to yield 6-hydroxy-1-methyl-2-phenylindole (117 mg, 524 ⁇ mol, 68 % of theory).
  • R1 means reactant 1
  • R2 means reactant 2
  • [P] means product No. 21a R1 R2 [P] 21b R1 R2 [P] 21c R1 R2 [P] 21d R1 R2 [P] 21e R1 R2 [P] 21f R1 R2 [P] 21g R1 R2 [P] 21h R1 R2 [P] 21i R1 R2 [P] 21j R1 R2 [P] 21k R1 R2 [P] 21l R1 R2 [P]
  • the corresponding aliphatic alcohol is dissolved in dry THF and the solution is cooled with an ice-bath. Triethylamine (4.00 equivs.) is added and the solution is stirred for a few minutes. Then acryloyl chloride or methacryloyl chloride (1.05 - 2.00 equivs.) is added at ice-bath temperature, while precipitating a colourless solid. The solution is stirred for several hours and is monitored via TLC. Upon completion of the reaction, the suspension is filtrated and washed with THF. The filtrate is evaporated under reduced pressure and purified via column chromatography using cyclohexane / ethyl acetate.
  • R means reactant
  • [P] means product No. 22a
  • [P] 22b R [P] 22c
  • [P] 22d R [P] 22e
  • 22f R [P] 22g
  • [P] R means reactant
  • the corresponding monomer is dissolved in dry N,N-dimethylformamide in a Schlenck-tube with a stirring bar.
  • the solution is degassed performing three times freeze-evacuate-thaw cycles.
  • azoisobutyronitrile AIBN, 0.05 equiv.
  • AIBN azoisobutyronitrile
  • the solution is cooled to room temperature and is then poured dropwise into cold methanol (100 ml methanol / 100 mg monomer) while stirring.
  • the precipitated polymer is collected on a frit or the solution is centrifuged several times to obtain the final polymer material.
  • a composition of 1 H-indol derivative M-N3 and methyl methacrylate, initiator azobisisobutyronitrile (0.04 eq) and crosslinker ethylene glycol dimethacrylate (0.1 - 0.4 eq) in different ratios is degassed by three freeze-pump-thaw cycles.
  • Two glass plates are coated with a polyethylene sheet and a 0.5 mm thick cell is created between the polyethylene sheets using a silicone rubber gasket.
  • the coated faces of the glass sheets are clipped together using spring clips with a syringe needle being placed between the gasket and the polyethylene sheets.
  • the cavity is then filled with the above formulation through the needle using a gastight syringe. Once the cavity is filled the syringe needle is removed, a final clip is used to seal the mould and the assembly is placed in an oven at 60°C for 24 hours before the oven is ramped to a temperature of 90°C for a period of 3 hours.
  • the moulds are allowed to cool to room temperature before the film is removed from the mould.
  • Example 25 photoinduced refractive index change and glass transition temperature
  • phase transition temperatures are determined with a TA Instruments Q2000 differential scanning calorimeter during heating in the second heating run with 20 K/min from -100 °C to 200 °C in a hermetic aluminum pans. Irradiations of the blanks are performed with a Coherent Avia 355-7000 UV-Laser. Common photoactive polymers that undergo refractive index change upon irradiation with UV-light exhibit glass transition temperatures as low as 34°C.
  • Polymer films for refractive index measurements are prepared by spin coating or drop casting from 1-8 wt% solutions of the polymers in chloroform onto silicon wafers or quartz plates.
  • the monomers are melted under vacuum.
  • Appropriate amounts of a radical initiator and cross-linker are mixed in and quickly filled into a heated polymerization chamber.
  • Cross-linked polymer plates are obtained.
  • Refractive index change is induced by irradiation at 340 - 365 nm.
  • the refractive indices (n) of the polymer films and blanks at 590 nm are measured on Schmidt+Haensch AR12 before and after irradiation.
  • the following table shows the refractive indices before and after irradiation as well as the change in refractive index (max. ⁇ n).

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Claims (16)

  1. Composés de formule (I)
    Figure imgb0656
     dans lesquels
    X est O, S ou NR0,
    Y est indépendamment les uns des autres O, S ou une liaison,
    n vaut 0 ou 1,
    m vaut 0 ou 1,
    n+m vaut 1 ou 2,
    -[B]- est choisi dans le groupe constitué par la formule (1) à la formule (4),
    Figure imgb0657
    Figure imgb0658
    Figure imgb0659
    Figure imgb0660
    X1, X2, X3, X4 sont chacun indépendamment les uns des autres CR' ou N,
    X5 est chacun indépendamment O, S, C=O ou NR0,
    X6, X7 sont chacun indépendamment CR' ou N,
    R est choisi indépendamment à chaque occurrence dans le groupe constitué par H, F, un groupement alkyle linéaire ou ramifié ayant de 1 à 8 atomes de C ou un groupement alkyle linéaire ou ramifié partiellement ou totalement fluoré ayant de 1 à 4 atomes de C,
    R' est choisi indépendamment à chaque occurrence dans le groupe constitué par H, F, un groupement alkyle linéaire ou ramifié, non halogéné, partiellement ou totalement halogéné ayant de 1 à 20 atomes de C, un groupement hydroxyalkyle linéaire ou ramifié ayant de 1 à 20 atomes de C, un groupement cycloalkyle non halogéné, partiellement ou totalement halogéné ayant de 3 à 6 atomes de C, un groupement alcoxy linéaire ou ramifié, non halogéné, partiellement ou totalement halogéné ayant de 1 à 20 atomes de C, un groupement thioalkyle linéaire ou ramifié, non halogéné, partiellement ou totalement halogéné ayant de 1 à 20 atomes de C,
    R0 est choisi indépendamment à chaque occurrence dans le groupe constitué par un groupement alkyle linéaire ou ramifié ayant de 1 à 10 atomes de C ou un groupement cycloalkyle ayant de 3 à 6 atomes de C,
    R1 est un groupement polymérisable choisi dans le groupe constitué par
    un groupement alcényle de formule (5),
    Figure imgb0661
     où
    X10 est choisi dans le groupe constitué par O, S, C(=O), C(=O)O,
    R5, R9, R10 sont choisis à chaque occurrence, indépendamment les uns des autres, dans le groupe constitué par H, F, un groupement alkyle linéaire ou ramifié, non fluoré, partiellement ou totalement fluoré ayant de 1 à 20 atomes de C ou aryle ayant de 6 à 14 atomes de C,
    c vaut 0 ou 1 ; et des groupements trialcoxysilyle ou dialcoxyalkylsilyle où les groupements alkyle et/ou alcoxy sont chacun indépendamment linéaires ou ramifiés ayant de 1 à 6 atomes de C ; et
    des groupements silyle de formule (6), (7) ou (8),
    Figure imgb0662
    Figure imgb0663
     où « alkyl » signifie à chaque occurrence, indépendamment les uns des autres, un groupement alkyle linéaire ou ramifié ayant de 1 à 6 atomes de C et l'astérisque "*" désigne à chaque occurrence, indépendamment les uns des autres, une liaison au bras de liaison [-R2-Y]n et/ou [Y-R2]m,
    -R2- est -(C(R)2)o- ou -(C(R)2)p-X8-(C(R)2)q-(X9)s-(C(R)2)r-(X10)t-(C(R)2)u-, où au moins un R est F ou un groupement alkyle linéaire ou ramifié partiellement ou totalement fluoré ayant de 1 à 4 atomes de C,
    ou
    un groupement cycloalkylène ayant 5 ou 6 atomes de C qui est substitué par au moins un R qui est F ou un groupement alkyle linéaire ou ramifié partiellement ou totalement fluoré ayant de 1 à 4 atomes de C,
    o est choisi dans le groupe constitué par de 1 à 20,
    X8, X9, X10 sont indépendamment à chaque occurrence O, S, ou NR0,
    s, t valent indépendamment à chaque occurrence 0 ou 1,
    p, q sont choisis indépendamment à chaque occurrence dans le groupe constitué par de 1 à 10,
    r, u sont choisis indépendamment à chaque occurrence dans le groupe constitué par de 0 à 10, où le nombre global d'atomes pour -(C(R)2)p-Xs-(C(R)2)q-(X9)s-(C(R)2)r-(X10)t-(C(R)2)u-, va jusqu'à 20 atomes,
    R3, R4, R5, R6 sont indépendamment à chaque occurrence R',
    R7 est R' dans le cas où m vaut 0 et
    R7 est R1 dans le cas où m vaut 1.
  2. Composés selon la revendication 1, dans lesquels -[B]- correspond à la formule (1) ou la formule (2).
  3. Composés selon la revendication 1 ou 2, dans lesquels X1, X3 et X4 dans les formules (1) ou (2) sont CR' et R' revêt indépendamment à chaque occurrence une signification telle qu'indiquée selon la revendication 1.
  4. Composés selon l'une ou plusieurs parmi les revendications 1 à 3, dans lesquels X2 est CR' et R' revêt une signification telle qu'indiquée selon la revendication 1.
  5. Composés selon l'une ou plusieurs parmi les revendications 1 à 4, dans lesquels au moins un R' au sein de X1, X2, X3, X4, X6, ou X7 dans les formules (1) à (4) n'est pas H.
  6. Composés selon l'une ou plusieurs parmi les revendications 1 à 5, dans lesquels n vaut 1 et m vaut 0, lesdits composés répondant à la formule (I')
    Figure imgb0664
     où R1, -R2-, Y, R3, R4, R5, R6, X, -[B]-, et R7 revêtent une signification telle qu'indiquée selon l'une des revendications 1 à 5.
  7. Composés selon l'une ou plusieurs parmi les revendications 1 à 5, dans lesquels n vaut 0 et m vaut 1, lesdits composés répondant à la formule (I'")
    Figure imgb0665
     où R1, -R2-, Y, R3, R4, R5, R6, X, -[B]- et R7 revêtent une signification telle qu'indiquée selon l'une des revendications 1 à 5.
  8. Composés selon l'une ou plusieurs parmi les revendications 1 à 5, dans lesquels n vaut 1 et m vaut 1, lesdits composés répondant à la formule (I"')
    Figure imgb0666
     où R1, -R2-, Y, R3, R4, R5, R6, X, -[B]- et R7 revêtent une signification telle qu'indiquée selon l'une des revendications 1 à 5.
  9. Composés selon l'une ou plusieurs parmi les revendications 1 à 8, dans lesquels -R2- est indépendamment à chaque occurrence -(C(R)2)o- ou -(C(R)2)p-X8-(C(R)2)q-(X9)s-(C(R)2)r-(X10)t-(C(R)2)u-, où au moins un R est F ou un groupement alkyle linéaire ou ramifié partiellement ou totalement fluoré ayant de 1 à 4 atomes de C et tous les autres R, o, X8, X9, X10, s, t, p, q, r, et u revêtent une signification telle qu'indiquée selon la revendication 1.
  10. Composés selon l'une ou plusieurs parmi les revendications 1 à 9, dans lesquels R1 est indépendamment à chaque occurrence un radical acryle ou méthacryle.
  11. Oligomère ou polymère, comprenant des composés polymérisés de formule (I) tels que décrits selon l'une ou plusieurs parmi les revendications 1 à 10.
  12. Composition, comprenant au moins un composé de formule (I) selon l'une ou plusieurs parmi les revendications 1 à 10 et/ou un oligomère ou polymère selon la revendication 11.
  13. Article comprenant au moins un composé polymérisé de formule (I) selon l'une ou plusieurs parmi les revendications 1 à 10 ou au moins un oligomère ou polymère selon la revendication 11.
  14. Article selon la revendication 13, ledit article étant une ébauche qui peut être transformée en un implant oculaire ou un implant oculaire, préférablement une lentille intraoculaire.
  15. Procédé de façonnage d'un article selon la revendication 13 ou 14, ledit procédé comprenant les étapes consistant à
    - mettre à disposition une composition comprenant au moins un composé de formule (I) selon l'une ou plusieurs parmi les revendications 1 à 10 et/ou un oligomère ou polymère selon la revendication 11 ;
    - façonner ensuite l'article de ladite composition.
  16. Procédé de modification des propriétés optiques d'un article selon la revendication 13 ou 14, ledit procédé comprenant les étapes consistant à
    - mettre à disposition un article selon la revendication 13 ou 14, et
    - exposer ensuite ledit article à un rayonnement ayant une longueur d'onde d'au moins 200 nm et d'au plus 1500 nm.
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EP3133065A1 (fr) 2015-08-21 2017-02-22 Merck Patent GmbH Composés de dispositifs optiquement actifs
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AU2020262316A1 (en) 2019-04-26 2021-12-23 AMO Ireland System and method
US20230203214A1 (en) 2020-05-20 2023-06-29 Merck Patent Gmbh Azacoumarin and azathiocoumarin derivatives for use in optically active devices
WO2022012798A1 (fr) 2020-07-15 2022-01-20 Merck Patent Gmbh Dispositifs optiquement actifs
EP4015512A1 (fr) 2020-12-16 2022-06-22 AMO Ireland Dispositifs optiquement actifs
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